酿造食醋中碳、氧同位素比值的测定及应用研究

以酿造食醋为研究对象,建立元素分析/连续流-稳定同位素比质谱法（EA/GasBench Ⅱ-IRMS）测定食醋总碳、水中氧同位素比值（δ13C和δ18O）的方法。通过优化稀释倍数与进样体积,得到δ13C值测定最佳条件为食醋稀释2倍,进样体积1.0 μL;通过优化平衡时间和样品体积,得到δ18O值测定时平衡时间为24 h,样品体积为500 μL。结果表明,在最佳条件下,食品样品碳同位素比测定值标准偏差（SD）值均＜0.30‰,氧的同位素比测定值的SD值均＜0.10‰,表明该测定方法的稳定性较好。山西食醋总碳δ13C值分布在-23.26‰～-20.80‰,水中氧的δ18O值在-5.66‰～-4.49‰;镇江食醋总碳δ13C值在-25.93‰～-20.70‰,水中氧的δ18O值在-8.35‰～-5.61‰;结合碳氧同位素比值分析,可以将山西老陈醋、镇江香醋和镇江陈醋区分开（P＜0.01）。     

Low δ(18)O Values of Nitrate Produced from Nitrification in Temperate Forest Soils

Analyses of δ(18)O of nitrate (NO(3)(-)) have been widely used in partitioning NO(3)(-) sources. However the δ(18)O value of NO(3)(-) produced from nitrification (microbial NO(3)(-)) is commonly estimated using the δ(18)O of environmental water and molecular oxygen in a 2:1 ratio. Here our laboratory incubation of nine temperate forest soils across a 1500 m elevation gradient demonstrates that microbial NO(3)(-) has lower δ(18)O values than the predicted using the 2:1 ratio (by 5.2-9.5‰ at low elevation sites), in contrast to previous reports showing higher δ(18)O values (up to +15‰) than their predicted values. Elevated δ(18)O values of microbial NO(3)(-) were observed at high elevation sites where soil was more acidic, perhaps due to accelerated O-exchange between nitrite, an intermediate product of nitrification, and water. Lower δ(18)O of microbial NO(3)(-) than the predicted and from previous observations suggests that the contribution of anthropogenic N inputs, such as fertilizer and atmospheric deposition, to a given ecosystem and the progress of denitrification in nitrogen removal are greater than we know. More than half of the δ(18)O of stream NO(3)(-) lower than the predicted value along the elevation gradient also indicate the impropriety using the 2:1 ratio for differentiating NO(3)(-) sources.     

The application of SNIF‐NMR and IRMS combined with C,H and O isotopes for detecting the geographical origin of Chinese wines

The regional origin of Chinese wines was investigated using two important complementary techniques, site‐specific natural isotopic fractionation nuclear magnetic resonance (SNIF‐NMR) and isotope ratio mass spectrometry (IRMS). Twenty samples from five different grape varieties were collected from north Xinjiang in 2009, along with 100 wine samples from five different regions during 2010–2013. The (D/H)_I and (D/H)_II in wine ethanol ranged from 95.10 to 102.86 ppm and from 115.99 to 126.39 ppm using SNIF‐NMR, respectively. The ¹³C/¹²C of wine ethanol and ¹⁸O/¹⁶O of wine water were detected using IRMS. The δ¹³C value (?23.36‰) in coastal regions was higher than that in continental regions (?27.75‰). The temperature is the key for δ¹³C value. The δ¹⁸O ranged from ?1.94 to 4.57‰. The δ¹⁸O values were only positive in north Xinjiang which had the arid climate and strong sunshine. No difference was found for isotope ratios for wines made from five different grape varieties in north Xinjiang. All data evaluated by principal component analysis and linear discriminant analysis showed that the best method to distinguish the regional wine origin correctly is a combination of (D/H)_I, (D/H)_II, R, δ¹³C and δ¹⁸O. Therefore, natural multi‐elemental isotope ratios are effective in contributing to wine quality control in the Chinese market.     

Biotic and abiotic pathways of phosphorus cycling in minerals and sediments: insights from oxygen isotope ratios in phosphate

A key question to address in the development of oxygen isotope ratios in phosphate (δ(18)O(p)) as a tracer of biogeochemical cycling of phosphorus in ancient and modern environments is the nature of isotopic signatures associated with uptake and cycling of mineral-bound phosphate by microorganisms. Here, we present experimental results aimed at understanding the biotic and abiotic pathways of P cycling during biological uptake of phosphate sorbed to ferrihydrite and the selective uptake of sedimentary phosphate phases by Escherichia coli and Marinobacter aquaeolei. Results indicate that a significant fraction of ferrihydrite-bound phosphate is biologically available. The fraction of phosphate taken up by E. coli attained an equilibrium isotopic composition in a short time (<50 h) due to efficient O-isotope exchange (between O in PO(4) and O in water; that is, actual breaking and reforming of P-O bonds) (biotic pathway). The difference in isotopic composition between newly equilibrated aqueous and residual sorbed phosphate groups promoted the ion exchange (analogous to isotopic mixing) of intact phosphate ions (abiotic pathway) so that this difference gradually became negligible. In sediment containing different P phases, E. coli extracted loosely sorbed phosphate first, whereas M. aquaeolei preferred Fe-oxide-bound phosphate. The presence of bacteria always imprinted a biotic isotopic signature on the P phase that was taken up and cycled. For example, the δ(18)O(p) value of loosely sorbed phosphate shifted gradually toward equilibrium isotopic composition. The δ(18)O(p) value of Fe-oxide-bound phosphate, however, showed only slight changes initially but, when new Fe-oxides were formed, coprecipitated/occluded phosphate retained δ(18)O values of the aqueous phosphate at the time of formation of new Fe oxides. Concentrations and isotopic compositions of authigenic and detrital phosphates did not change, suggesting that these phosphate phases were not utilized by bacteria. These findings support burgeoning applications of δ(18)O(p) as a tracer of phosphorus cycling in sediments, soils, and aquatic environments and as an indicator of paleo- environmental conditions.     

δ18O of Ethanol in Wine and Spirits for Authentication Purposes

Since 1986 the European Union has established official isotopic analysis methods for detecting the illegal addition of sugar and water to wine and to enable geographical traceability. In this paper we investigate the possibility of using analysis of the ¹⁸O/¹⁶O stable isotope ratio (expressed as δ¹⁸O) of ethanol to improve detection of the watering of wine and to determine the origin of ethanol. Sixty‐nine authentic wine samples from all over Italy, 59 spirits from fruit and cereals, 5 chemically synthesized ethanols, one concentrated and rectified must, one beet and one cane sugar, one fresh must, and 6 waters with increasing δ¹⁸O values were considered. Ethanol was recovered by distillation, using a Cadiot spinning band column, following the official OIV methods. The residual water was trapped by storing the distillate for at least 24 h on a molecular sieve. The ¹⁸O/¹⁶O ratio was measured using a pyrolyser interfaced with an isotope ratio mass spectrometer. The δ^‐18O of ethanol is significantly related to the δ¹⁸O of the fermentation water and can be considered as a reliable internal reference. The values ranged from +24‰ to +36‰ in wine (years 2008 to 2012), +10‰ to +26‰ in fruit and cereal distillates, and from –2‰ to +12‰ in synthetic ethanol. The method was shown to be effective in improving detection of the watering of wine and determining the origin of ethanol (from grapes, other fruit, or synthesis), but not in detecting the addition of cane or beet sugar to wine.     

Chlorine and carbon isotopes fractionation during volatilization and diffusive transport of trichloroethene in the unsaturated zone

To apply compound-specific isotope methods to the evaluation of the origin and fate of organic contaminants in the unsaturated subsurface, the effect of physicochemical processes on isotope ratios needs to be known. The main objective of this study is to quantify chlorine and carbon isotope fractionation during NAPL-vapor equilibration, air-water partitioning, and diffusion of trichloroethene (TCE) and combinations of these effects during vaporization in porous media. Isotope fractionation is larger during NAPL-vapor equilibration than air-water partitioning. During NAPL-vapor equilibration, carbon, and chlorine isotope ratios evolve in opposite directions although both elements are present in the same bond, with a normal isotope effect for chlorine (ε(Cl) = -0.39 ± 0.03‰) and an inverse effect for carbon (ε(C) = +0.75 ± 0.04‰). During diffusion-controlled vaporization in a sand column, no significant carbon isotope fractionation is observed (ε(C) = +0.10 ± 0.05‰), whereas fairly strong chlorine isotope fractionation occurs (ε(Cl) = -1.39 ± 0.06‰) considering the molecular weight of TCE. In case of carbon, the inverse isotope fractionation associated with NAPL-vapor equilibration and normal diffusion isotope fractionation cancel, whereas for chlorine both processes are accompanied by normal isotope fractionation and hence they cumulate. A source of contamination that aged might thus show a shift toward heavier chlorine isotope ratios.     

Isotope fractionation of selenium during fungal biomethylation by Alternaria alternata

The natural abundance of stable Se isotopes may reflect sources and formation conditions of methylated Se. We aimed at (1) quantifying the degree of methylation of selenate [Se(VI)] and (hydro)selenite [Se(IV)] by the fungus Alternaria alternata at pH 4 and 7 and (2) determining the effects of these different Se sources and pH values on 82Se/76Se ratios (δ82/76Se) in methylselenides. Alternaria alternata was incubated with Se(VI) and Se(IV) in closed microcosms for 11-15 days and additionally with Se(IV) for 3-5 days at 30 °C. We determined Se concentrations and δ82/76Se values in source Se(VI) and Se(IV), media, fungi, and trapped methylselenides. In Se(VI) incubations, methylselenide volatilization ended before the 11th day, and the amounts of trapped methylselenide were not significantly different among the 11-15 day incubations. In 11-15 days, 2.9-11% of Se(VI) and 21-29% of Se(IV) were methylated, and in 3-5 days, 3-5% of Se(IV) was methylated. The initial δ82/76Se values of Se(VI) and Se(IV) were -0.69±SD 0.07‰, and -0.20±0.05‰, respectively. The δ82/76Se values of methylselenides differed significantly between Se(VI) (-3.97‰ to -3.25‰) and Se(IV) (-1.44‰ to -0.16‰) as sources after 11-15 days of incubation; pH had little influence on δ82/76Se values. Thus, the δ82/76Se values of methylselenide indicate the source species of methylselenides used in this study. The strong isotope fractionation of Se(VI) is probably attributable to the different reduction steps of Se(VI) to Se(-II) which were rate-limiting explaining the low methylation yields, but not to the methylation itself. The shorter incubation of Se(IV) for 3-5 days showed a large Se isotope fractionation of at least -6‰ before the biomethylation reaction reached its end. This initial Se isotope fractionation during methylation of Se(IV) is much larger than previously published.     

Mercury stable isotopes in seabird eggs reflect a gradient from terrestrial geogenic to oceanic mercury reservoirs

Elevated mercury concentrations ([Hg]) were found in Alaskan murre (Uria spp.) eggs from the coastal embayment of Norton Sound relative to insular colonies in the northern Bering Sea-Bering Strait region. Stable isotopes of Hg, carbon, and nitrogen were measured in the eggs to investigate the source of this enrichment. Lower δ(13)C values in Norton Sound eggs (-23.3‰ to -20.0‰) relative to eggs from more oceanic colonies (-20.9‰ to -18.7‰) indicated that a significant terrestrial carbon source was associated with the elevated [Hg] in Norton Sound, implicating the Yukon River and smaller Seward Peninsula watersheds as the likely Hg source. The increasing [Hg] gradient extending inshore was accompanied by strong decreasing gradients of δ(202)Hg and Δ(199)Hg in eggs, indicating lower degrees of mass-dependent (MDF) and mass-independent Hg fractionation (MIF) (respectively) in the Norton Sound food web. Negative or zero MDF and MIF signatures are typical of geological Hg sources, which suggests murres in Norton Sound integrated Hg from a more recent geological origin that has experienced a relatively limited extent of aquatic fractionation relative to more oceanic colonies. The association of low δ(202)Hg and Δ(199)Hg with elevated [Hg] and terrestrial δ(13)C values suggested that Hg stable isotopes in murre eggs effectively differentiated terrestrial/geogenic Hg sources from oceanic reservoirs.     

SNIF-NMR和IRMS技术在原产地葡萄酒鉴定中的应用

利用点特异性天然同位素分馏核磁共振技术(SNIF-NMR)和同位素比质谱仪(IRMS)技术测定葡萄酒中稳定性同位素D/H、18O/16O和13C/12C的比值,结果表明(D/H)Ⅱ、R、δ18O‰对产地的鉴别提供着主要信息,而(D/H)Ⅰ与δ13C‰提供了较次要的信息,单独使用SNIF-NMR结果只能区别开环境差异很大的地区,加上δ13C‰后,可将温差大的地区区别开,但对环境相似的地区仍无法有效鉴别,最后将(D/H)Ⅱ、R、δ13C‰、δ18O‰同时考虑,对于环境相似的地区也可以有效鉴别。研究结果为中国葡萄酒原产地鉴别提供了一种新的技术手段。     

Demonstrating a natural origin of chloroform in groundwater using stable carbon isotopes

Chloroform has been for a long time considered only as an anthropogenic contaminant. The presence of chloroform in forest soil and groundwater has been widely demonstrated. The frequent detection of chloroform in groundwater in absence of other contaminants suggests that chloroform is likely produced naturally. Compound-specific isotope analysis of chloroform was performed on soil-gas and groundwater samples to elucidate whether its source is natural or anthropogenic. The δ(13)C values of chloroform (-22.8 to -26.2‰) present in soil gas collected in a forested area are within the same range as the soil organic matter (-22.6 to -28.2‰) but are more enriched in (13)C compared to industrial chloroform (-43.2 to -63.6‰). The δ(13)C values of chloroform at the water table (-22.0‰) corresponded well to the δ(13)C of soil gas chloroform, demonstrating that the isotope signature of chloroform is maintained during transport through the unsaturated zone. Generally, the isotope signature of chloroform is conserved also during longer range transport in the aquifer. These δ(13)C data support the hypothesis that chloroform is naturally formed in some forest soils. These results may be particularly relevant for authorities' regulation of chloroform which in the case of Denmark was very strict for groundwater (<1 μg/L).     

Effect of different carbon substrates on nitrate stable isotope fractionation during microbial denitrification

In batch experiments, we studied the isotope fractionation in N and O of dissolved nitrate during dentrification. Denitrifying strains Thauera aromatica and "Aromatoleum aromaticum strain EbN1" were grown under strictly anaerobic conditions with acetate, benzoate, and toluene as carbon sources. (18)O-labeled water and (18)O-labeled nitrite were added to the microcosm experiments to study the effect of putative backward reactions of nitrite to nitrate on the stable isotope fractionation. We found no evidence for a reverse reaction. Significant variations of the stable isotope enrichment factor ε were observed depending on the type of carbon source used. For toluene (ε(15)N, -18.1 ± 0.6‰ to -7.3 ± 1.4‰; ε(18)O, -16.5 ± 0.6‰ to -16.1 ± 1.5‰) and benzoate (ε(15)N, -18.9 ± 1.3‰; ε(18)O, -15.9 ± 1.1‰) less negative isotope enrichment factors were calculated compared to those derived from acetate (ε(15)N, -23.5 ± 1.9‰ to -22.1 ± 0.8‰; ε(18)O, -23.7 ± 1.8‰ to -19.9 ± 0.8‰). The observed isotope effects did not depend on the growth kinetics which were similar for the three types of electron donors. We suggest that different carbon sources change the observed isotope enrichment factors by changing the relative kinetics of nitrate transport across the cell wall compared to the kinetics of the intracellular nitrate reduction step of microbial denitrification.     

Online stable isotope analysis of dissolved organic carbon size classes using size exclusion chromatography coupled to an isotope ratio mass spectrometer

Stable isotopic content of dissolved organic carbon (δ(13)C-DOC) provides valuable information on its origin and fate. In an attempt to get additional insights into DOC cycling, we developed a method for δ(13)C measurement of DOC size classes by coupling high-performance liquid chromatography (HPLC)-size exclusion chromatography (SEC) to online isotope ratio mass spectrometry (IRMS). This represents a significant methodological contribution to DOC research. The interface was evaluated using various organic compounds, thoroughly tested with soil-water from a C3-C4 vegetation change experiment, and also applied to riverine and marine DOC. δ(13)C analysis of standard compounds resulted in excellent analytical precision (≤0.3‰). Chromatography resolved soil DOC into 3 fractions: high molecular weight (HMW; 0.4-10 kDa), low molecular weight (LMW; 50-400 Da), and retained (R) fraction. Sample reproducibility for measurement of δ(13)C-DOC size classes was ±0.25‰ for HMW fraction, ± 0.54‰ for LMW fraction, and ±1.3‰ for R fraction. The greater variance in δ(13)C values of the latter fractions was due to their lower concentrations. The limit of quantification (SD ≤0.6‰) for each size fraction measured as a peak is 200 ng C (2 mg C/L). δ(13)C-DOC values obtained in SEC mode correlated significantly with those obtained without column in the μEA mode (p < 0.001, intercept 0.17‰), which rules out SEC-associated isotopic effects or DOC loss. In the vegetation change experiment, fractions revealed a clear trend in plant contribution to DOC; those in deeper soils and smaller size fractions had less plant material. It was also demonstrated that the technique can be successfully applied to marine and riverine DOC without further sample pretreatment.     

Zinc isotopic composition of particulate matter generated during the combustion of coal and coal + tire-derived fuels

Atmospheric Zn emissions from the burning of coal and tire-derived fuel (TDF) for power generation can be considerable. In an effort to lay the foundation for tracking these contributions, we evaluated the Zn isotopes of coal, a mixture of 95 wt % coal + 5 wt % TDF, and the particulate matter (PM) derived from their combustion in a power-generating plant. The average Zn concentrations and δ(66)Zn were 36 mg/kg and 183 mg/kg and +0.24‰ and +0.13‰ for the coal and coal + TDF, respectively. The δ(66)Zn of the PM sequestered in the cyclone-type mechanical separator was the lightest measured, -0.48‰ for coal and -0.81‰ for coal+TDF. The δ(66)Zn of the PM from the electrostatic precipitator showed a slight enrichment in the heavier Zn isotopes relative to the starting material. PM collected from the stack had the heaviest δ(66)Zn in the system, +0.63‰ and +0.50‰ for the coal and coal + TDF, respectively. Initial fractionation during the generation of a Zn-rich vapor is followed by temperature-dependent fractionation as Zn condenses onto the PM. The isotopic changes of the two fuel types are similar, suggesting that their inherent chemical differences have only a secondary impact on the isotopic fractionation process.     

Higher mass-independent isotope fractionation of methylmercury in the pelagic food web of Lake Baikal (Russia)

Mercury undergoes several transformations that influence its stable isotope composition during a number of environmental and biological processes. Measurements of Hg isotopic mass-dependent (MDF) and mass-independent fractionation (MIF) in food webs may therefore help to identify major sources and processes leading to significant bioaccumulation of methylmercury (MeHg). In this work, δ(13)C, δ(15)N, concentration of Hg species (MeHg, inorganic Hg), and stable isotopic composition of Hg were determined at different trophic levels of the remote and pristine Lake Baikal ecosystem. Muscle of seals and different fish as well as amphipods, zooplankton, and phytoplankton were specifically investigated. MDF during trophic transfer of MeHg leading to enrichment of heavier isotopes in the predators was clearly established by δ(202)Hg measurements in the pelagic prey-predator system (carnivorous sculpins and top-predator seals). Despite the low concentrations of Hg in the ecosystem, the pelagic food web reveals very high MIF Δ(199)Hg (3.15-6.65‰) in comparison to coastal fish (0.26-1.65‰) and most previous studies in aquatic organisms. Trophic transfer does not influence MIF signature since similar Δ(199)Hg was observed in sculpins (4.59 ± 0.55‰) and seal muscles (4.62 ± 0.60‰). The MIF is suggested to be mainly controlled by specific physical and biogeochemical characteristics of the water column. The higher level of MIF in pelagic fish of Lake Baikal is mainly due to the bioaccumulation of residual MeHg that is efficiently turned over and photodemethylated in deep oligotrophic and stationary (i.e., long residence time) freshwater columns.     

Using ¹⁷O to investigate nitrate sources and sinks in a semi-arid groundwater system

We apply a triple isotope approach for nitrate that utilizes Δ(17)O as a conservative tracer, in combination with δ(18)O and δ(15)N, to assess source/sink dynamics of groundwater nitrate beneath alluvial washes in a semiarid urban setting. Other studies have used δ(18)O and δ(15)N to determine nitrate sources and cycling, but the atmospheric δ(18)O signature can be overprinted by biogeochemical processes. In this study, δ(18)O and δ(15)N values of nitrate were coupled with δ(17)O values of nitrate to quantify atmospheric nitrate inputs and denitrification amounts. Results show generally low groundwater nitrate concentrations (<0.2 mmol/L) throughout the basin; high nitrate concentrations (up to 1 mmol/L) with evidence for some denitrification were detected in areas where effluent was the predominant source of recharge to groundwater. Furthermore, the denitrification was inferred from elevated δ(18)O and δ(15)N values which were reinforced by increases in observed δ(17)O values. Finally, relatively low, but significant atmospheric nitrate concentrations were measured in groundwater (up to 6% of total nitrate). This study concludes that the triple isotope approach improves determination of the proportion of atmospheric nitrate and the significance of denitrification in natural waters, allowing us to develop a conceptual model of the biogeochemical processes controlling nitrogen in an urban setting.     

Isotopic character of nitrous oxide emitted from streams

Global models have indicated agriculturally impacted rivers and streams may be important sources of the greenhouse gas nitrous oxide (N(2)O). However, there is significant uncertainty in N(2)O budgets. Isotopic characterization can be used to help constrain N(2)O budgets. We present the first published measurements of the isotopic character of N(2)O emitted from low (2-4) order streams. Isotopic character of N(2)O varied seasonally, among streams, and over diel periods. On an annual basis, δ(18)O of emitted N(2)O (+47.4 to +51.4‰; relative to VSMOW) was higher than previously reported for larger rivers, but δ(15)N of emitted N(2)O (-16.2 to +2.4‰ among streams; relative to atmospheric N(2)) was similar to that of past studies. On an annual basis, all streams emitted N(2)O with lower δ(15)N than tropospheric N(2)O. Given these streams have elevated nitrate concentrations which are associated with enhanced N(2)O fluxes, this supports the hypothesis that streams are contributing to the accumulation of (15)N-depleted N(2)O in the troposphere.     

Isotopic disequilibrium during uptake of atmospheric CO2 into mine process waters: implications for CO2 sequestration

Dypingite, a hydrated Mg-carbonate mineral, was precipitated from high-pH, high salinity solutions to investigate controls on carbon fixation and to identify the isotopic characteristics of mineral sequestration in mine tailings. δ(13)C values of dissolved inorganic carbon content and synthetic dypingite are significantly more negative than those predicted for equilibrium exchange of CO(2) gas between the atmosphere and solution. The measured δ(13)C of aqueous carbonate species is consistent with a kinetic fractionation that results from a slow diffusion of atmospheric CO(2) into solution. During dypingite precipitation, dissolved inorganic carbon concentrations decrease and δ(13)C values become more negative, indicating that the rate of CO(2) uptake into solution was outpaced by the rate of carbon fixation within the precipitate. This implies that CO(2) gas uptake is rate-limiting to CO(2) fixation. δ(13)C of carbonate mineral precipitates in mine tailings and of DIC in mine process waters display similar (13)C-depletions that are inconsistent with equilibrium fractionation. Thus, the rate of carbon fixation in mine tailings may also be limited by supply of CO(2). Carbon sequestration could be accelerated by increasing the partial pressure of CO(2) in tailings ponds or by using chemicals that enhance the uptake of gaseous CO(2) into aqueous solution.     

Oxygen isotopes unravel the role of microorganisms in phosphate cycling in soils

Phosphorus (P) is considered the ultimate limiting nutrient for plants in most natural systems and changes in the distribution of inorganic and organic P forms during soil development have been well documented. In particular, microbial activity has been shown to be an important control on P cycling but its contribution in building up the pool of plant-available P during soil development is still poorly quantified. To determine the importance of different biological processes on P cycling, we analyzed the isotopic composition of oxygen in phosphate (δ(18)O-Pi) from the parent material, soil microorganisms, the available P pool, and from the vegetation along a 150-year soil chronosequence of a glacier forefield. Our results show that at all sites, δ(18)O-Pi of microbial Pi is within the range expected for the temperature-dependent equilibrium between phosphate and water. In addition, the isotopic signature of available Pi is close to the signature of microbial Pi, independently of the contribution of parent material Pi, vegetation Pi or Pi released from organic matter mineralization. Thus, we show that phosphate is cycled through soil microorganisms before being released to the available pool. This isotopic approach demonstrates for the first time in the field and over long time scales, and not only through controlled experiments, the role of the microbial activity in cycling of P in soils.     

Measurement of stable isotope abundances in milk and milk ingredients — a possible tool for origin assignment and quality control

Relative carbon and nitrogen stable isotope abundances in total milk reflect the isotopic composition of the diet fed to the dairy cows; this diet and its δ-values depend on geographical and climatic factors. Milk from regions dominated by grassland typically shows relatively negative δ¹³C-values, while in regions dominated by crop cultivation the δ¹³C-values are more positive. The δ¹⁵N-values are influenced by factors such as soil conditions, the intensity of agricultural use and the climate. Casein in authentic milk samples is enriched in both ¹³C and ¹⁵N as compared to total milk, while the whey fraction is slightly enriched in ¹³C and depleted of ¹⁵N. The isotopic content of milk, casein and whey from one location have been measured throughout a period of longer than 1 year; variations are usually not greater than 1‰. In milk water, the ¹⁸O content was increased by between 2 and 6‰ as compared to ground water.     

Tracing sources and bioaccumulation of mercury in fish of Lake Baikal--Angara River using Hg isotopic composition

This study presents the determination and comparison of isotopic compositions of Hg in sediments, plankton, roach, and perch of two freshwater systems in the Lake Baikal-Angara River aquatic ecosystem: the man-made Bratsk Water Reservoir contaminated by Hg from a chlor-alkali factory and the noncontaminated Lake Baikal. Isotopic ratios of biota exhibit both significant mass-independent fractionation (MIF) (Δ(199)Hg from 0.20 to 1.87‰) and mass-dependent fractionation (MDF) (δ(202)Hg from -0.97 to -0.16‰), whereas sediments exhibit high MDF (δ(202)Hg from -1.99 to -0.83‰) but no MIF. δ(15)N and δ(13)C are correlated with methylmercury in organisms from both sites, indicating bioaccumulation and biomagnification through food webs of both regions. Combining this with isotopic composition of samples shows that δ(202)Hg increases with the trophic level of organisms and also with methylmercury in fish from Lake Baikal. This study demonstrates that MIF in fish samples from Bratsk Water Reservoir allow to trace anthropogenic Hg, since fish with the highest levels of Hg in muscle have the same isotopic composition as the sediment in which anthropogenic Hg was deposited. Less contaminated fish do not exhibit this anthropogenic signature accumulating relatively lower Hg amount from the contaminated sediments. This work reveals that Hg isotopic composition can be used to track the contribution of anthropogenic sources in fish from a contaminated lake.